Tetrahydrophthalic acid half ester compounds



Patented Oct. 13,1953

UNITED STLTS PATENT GFFICE z;s55,4s7

im i Alefander K yi; 4ensevilre, and Entert Geil'sgDoWnersdGfve, Ill.,assignors to Fredk A. StleselRtegfIne., a corporation of IllinoisNUDI-swing. mutation selifeniber' 27, 195o, sermrNo. 187,130

hexyl, methyl cyclopentyl; or an alkyl radical alf estercoxrntioundsuofn polyhydroxy having l to 16 (or an alkenyl radicalhaving 2 to y stantiauy `Statie oily ninas useful as) suon; `as

pounds. This invention further' relates to a 10 p'la'stieizersL`wettinghants;eilsifyingfagerits vennen navette followingstructufallformula; 16 ofur col-pen' 111g gppnation" serial Nd: 187,126

med-onevenfdateherwitn,

n It is' known in 'the 'art tdform alky'dtype resins bjyfv reactionpfgiytrihe or monbglyceridesf with] tetrahydroplithalic acid as'taugftin U. S. Patent H 20 1,860,730. However,l therea'otionlofsehcoinponentsis rapidand uncontrollableto form resin- I R`CH`O` "CH CH ousproducts ofaindenite structure and uncontrollable charateristics.Moreover, ithas been a l suggestedbv'nielswdrmhf1928iwofre 98.: 25CheniLAb's". 1928; 22; 11A"44`to react Inaleie anhyund with 1,3Abatadienej tgiprpque tetrenrgerqor the isomeric strutture" whereinsmbitii half ester is upon a different.hydroxyl:` 30

produce this "compound l o 205g# According to the meth'od of thisinvention we v \'ry first produce a mono fatty acid ester of apolyn-lf-*oeffe-H 0H R'-cH-oH-`oj` f l 35 cation containing at least twofree hydroxyl H;O(lj iff gr'tnips.` This product is then-reacted withmaleic /f or fu'znarie acid or the anhydrid thereof to form CF1' a halfester having uat least one free hydroxyl It andfone" reoa'rboxylradioal. half` esterd `3l1ikyih DMS-elder Sinfhsftdp 'Off 1.11?@1112 Teesly: contained `te; a'f'tion,l 'the tetra ydrophthlic aeidderivatives of thepre'st if'rt. 4 I y 1. Formation "of mooffatty-aei'et`e`r of' polyhil/drbyl-aliplzatic zlcohol Asidiegtea'abtv t anyjptlytyartyiaiiphafic aIcohOTWtli `th""s'o15"of the 'fonulaf may`additionally be substitutedfvvith upf-to three` 50` Rf' n RaoHLoonfalkyl substituents;` such as phenyl, toluyl,` eyclo- 55'r wherein R'isuhydrogenor a 1 tot carbon atoxnA wherein R `is the alkyl, `alkenyl,Horl hydroxy alkenyl typical long-chainresidue of;saturated` additionallycontain up to 3 distributed not more than one hydroxyl for each carbonatom, such as glycerine, mannitol, sorbitol, pentaerythritol, and themethyl, ethyl or propyl derivatives thereof is re-V acted with a fattyacid to form the monoester. A preferred source of materials from whichmono fatty esters of the polyhydroxy alcohol is formed is naturaloccurring triglycerides of the fixed oils of commerce. Such fixed oilsare fish oil, lard, stearin, palm oil, cocoanut oil, soy bean oil, tungoil, linseed oil, oiticica oil, and castor oil, which may be convertedto the monoglyceride preferably by the following reaction:

alkyl which may hydroxyl groups o CH2O UJ-R cHl-o-H Fixed oil GlycerineOther known methods of forming monoglycerides such as by directesterification of any polyhydric alcohol with a fatty acid or compoundthereof may be used or a different polyhydric alcohol may be substitutedfor glycerine in the above reaction to give a mixture of mono fatty acidesters with different alcohols. Similarly a mixture of triglycerideshaving different fatty acids may be reacted with glycerine to obtain amixture of monoglycerides having different fatty acid radicals. Thisreaction to form the monoglyceride is effected by heating 2 mois ofglycerine with one mol of triglyceride at a temperature of 425 to 450 F.preferably about 440 F. for a period of several hours such as 3 to 6hours, with constant stirring and preferably in an inert atmosphere suchas carbon dioxide or nitrogen.

2. Formation of maleic or fumarie half ester of the mono fatty ester Themono fatty ester as described above is then reacted with maleic orfumarie acid or anhydride, preferably maleic anhydride, to form a halfester according to the following reaction:

Ha- O -H Monoglycerde In this reaction R and R have the samesignificance listed above, and either fumarie or maleic acid may besubstituted for the maleic anhydride. In effecting the reaction equalmolar proportions of the maleic anhydride and mono fatty acid ester areheated together at a temperature of 150 to 180 F. for a period of 1 to 5hours, the exact end point being determined by measuring the acidnumber, which may be calculated from the formula of the compound to beobtained. For example, a non-conjugated fatty acid monoglyceride withapproximately a 16 carbon atom fatty acid reacted with maleic anhydridehas a theoretical acid value for the half ester of 123. In thistemperature range of about 150 to 180 F. the maleic carboxyl radicaltends to esterify group in the 3 position with respect to the fattyglyceride and, reacting at the upper end of such range, about 180 F.,such isomer is obtained almost exclusively. Some esterification, up toabout 20% of the total half ester produced, will takeY place on thehydroxyl in the 2 position with respect to the fatty glyceride when thereaction is run at the lower end of the temperature range, at about 150F. Thus in the reaction on monoglycerides over the temperature rangegiven, a mixture of half ester isomers may be obtained containing up toabout 20% of esters in the 2 hydroxyl position. Where the alcoholcontains more than three hydroxyls, maleic half esters in the 3 positionof the polyhydric alcohol will predominate, but the half ester productwill contain minor proportions of isomeric maleic half esters on otherhydroxyl positions.

` 3. Formation of the tetrahydrophthalic acid half ester 'I'he maleicfatty acid half ester obtained as described above is reacted with a 1,3diene to obtain in an easily controlled Bicis-Alder condensation, thetetrahydrophthalic acid half ester intermediate of the presentinvention. The following equation illustrates this reaction:

only the hydroxyl H Grifo-CAR acid half ester Where R, R', R" and X havethe significance given above. In this instance R '-CHzCH-CHICHX is the1-3 dienic derivative of the radicals listed above for R and includessuch specific compounds as 4-phenyl butadiene 1-3, 4-p toluyl butadiene1-3, li-cyclohexyl butadiene 1-3, 4-(2 methyl cyclo pentyl) butadiene1-3, butadiene 1-3, l-chloro pentadiene 13, 4iso propyl butadiene 1-3,hexadiene 1-3, di isobutyl butadiene 1-3, heptadiene 1-3, octadiene L3,1-bromo pentadiene 1-3, 4-dodecyl butadiene 1-3, and octadecyl butadiene1-3. Y

The reaction between the 1-3 diene and the maleic half ester is effectedby mixing the diene and the maleic acid half ester in equirnclarproportions, and heating the mixture at a moderate temperature of about85 to 150 F., preferably 115 to 125 F. over a period of 2 to 48 hours.The reaction time will vary with applied pressure, and becomesconsiderably shorter at higher pressures. For example, practicalpressures of 2 to 30 pounds per square inch (p. s. i.) are the usualrange for commercially available auto claves. Higher pressures up to p.s. i. may be used in more expensive equipment capable of withstandingsuch pressure. In general it is carry out the reaction in thetemperature range given at a pressure 10 to 30 p. s. i. over a period of3 to 40v hours, usually about 5 to v10 hours, for maximum economy andyields.

-The reaction vessel may be made of any usual .in the range of 225 to400 ats-5,4@

metal such as taining as a gas, to the reaction mixture as the reactionproceeds.

Such product dissolved to a 70% solution in xylene has a color` value of`8 (Gardner) and a viscosity of A-l (Gardner-Holdt).

This intermediate has a wide utility for various uses.

normal temperatures but can densed to an alkyd type resinous `body.

4. Formation of resin ,from half ester As pointed out in ourabove-mentioned corated petroleum naphtha having a boiling point F. aresuitable solvents for azeotropic resin` formation.

In effecting the resinification of the intermedil ,l I.Other -knownmethods of azet'ropic distillahigh pressure steam distillation tion suchas a reaction conditions which has Widely variable uses. Theintermediate is capable of modification Aas to the type of EXAMPLE i a.Fatty acids obtained 'by is'aponication of soy bean oil with a 10%sodium hydroxide Vsolution and subsequent acidification withhydroviscosity of V- (Gardner-Holdt) and a color of 11 (Gardner).

(Gardner) `acid value -mately 334" to yield a Vhalf ester with a 1.3diene to solution of resin in xylene. The resin solution obtained afterdistilling for two hours had a viscosity of A-l (Gardner-Boldt) a colorof 9-10 (Gardner) and an acid value of 12. To the solution of 48% non- 5volatile resinied solids in xylene, a drier comprising a mixture of a0.5% lead naphthenate and 0.05% cobalt naphthenate based upon thenon-volatile solids was added. The solution was then distributed as afilm on glass and air dried. The film was slight tack to paper after sixhours and was tack free to paper in 24 hours. The film was transparentand comprised the self polymer-ized intermediate of tetrahydrophthalicacid and soy bean oil fatty acid monoglyceride.

EXAMPLE II A similar procedure as set forth in Example I was used toprepare an intermediate tetrahydrophthalic acid and linseed oil fattyacids. The product was resinified to an alkyd resin by condensation inthe manner described in Example 1 and it dried tack-free to paper in 12hours and had only a slight tack in 31/2 hours, similarly using astandard drier.

The resin of the present invention, itself, as indicated above, issubject to considerable modithe fatty acid and the specific polyhydricalcohol and with Various derivatives of tetrahydrophthalic acid. It isaccordingly intended that the examples given herein be regarded asillustrative and not limiting except as defined in the claims appendedhereto.

We claim:

1. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a mono 12 to 22 carbon atom fatty acidester of a polyhydroxy aliphatic alcohol having at least two freehydroxyl groups with one carboxyl radical of an acid selected from thegroup consisting of maleic acid, fumarie acid and anhydridcs thereof toform a half ester therewith, and then condensing Said half ester with a1,3 diene to form a tetrahydrophthalic acid half ester containing atleast one free hydroxyl radical and one free carboxyl radical.

2. The method of forming a tetrahydrophthalic acid half ester of a fattyacid monoglyceride comprising condensing a 12 to 22 carbon atom fattyacid monoglyceride half ester of maleic acid containing at least onefree hydroxyl radical and one free carboxyl radical with a 1,3 diene.

3. The method of forming a tetrahydrophthalic acid half ester of a fattyacid monoglyceride comprising condensing a 12 to 22 carbon atom fattyacid monoglyceride half ester of maleic acid containing at least onefree hydroxyl radical and one free carboxyl radical With 1,3 butadiene.

4. The method of forming an alkyd resin comprising dissolving atetrahydrophthalic acid half ester of a 12 to 22 carbon atom fatty acidmonoester of a polyhydroxy aliphatic alcohol having at least one freehydroxyl group and one free carboxyl groupV in a solvent and heating thesolution and thereby azeotropically distilling said solvent and water ofcondensation from the solution.

5. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a linseed oil fatty acid monoglyceridewith one carboxyl radical of an acid selected from the group consistingof maleic acid, fumarie acid and anhydrides thereof to form a half estertherewith, and then condensing said forma tetrahydro- 75 phthalic acidhalf ester containing at least one free hydroxyl radical and one freecarboxyl radical.

6. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a mono l2 to 22 carbon atom fatty acidester of a polyhydroxy aliphatic alcohol having atleast two freehydroxyl groups with one carboxyl radical of an acid selected from thegroup consisting of maleic acid, fumarie acid and anhydrides thereof toform a half ester therewith, and then condensing said half ester with1,3, butadiene to form a tetrahydrophthalic acid half ester containingatleast one free hydroxyl radical and one free carboxyl radical. Y Y

'1. The method of forming a tetrahydrophthalic acid half ester of afatty acid monoglyceride comprising condensing a 12 to 22 carbon atomfatty acid monoglyceride half ester of an acid selected from the groupconsisting of rnaleic acid, fumarie acid and anhydrides thereof,containing at least one free hydroxyl radical and one free carboxylradical, with a 1,3 diene.

3. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a soy bean oil fatty acid monoglyceridewith one carboxyl radical of an acid selected from the group consistingof maleic acid, fumarie acid and anhydrides thereof to form a halfeste-r therewith, and then condensing said half ester with a 1,3 dieneto form a tetrahydrophthalic acid half ester containing at least onefree hydroxyl radical and one free carboxyl radical.

9. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a tung oil fatty acid monoglyceride withone carboxyl radical of an acid selected from the group consisting ofmaleic acid, fumaric acid and anhydrides thereof to form a half estertherewith, and then condensing said half ester with a 1,3 diene to forma tetrahydrophthalic acid half ester containing at least one freehydroxyl radical and one free carboxyl radical.

10. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a castor oil fatty acid monoglyceridewith one carboxyl radical of an acid selected from the group consistingof maleic acid, fumarie acid and anhydrides thereof to form a half estertherewith, and then condensing said half ester with a 1,3 diene to forma tetrahydrophthalic acid half ester containing at least one freehydroxyl radical and one free carboxyl radical.

11. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a cocoanut oil fatty acid monoglycerdewith one carboxyl radical of an acid selected from the group consistingof maleic acid, fumarie acid and anhydrides thereof to form a half estertherewith, and then condensing said half ester with a 1,3 diene to forma tetrahydrophthalic acid half ester containing at least one freehydroxyl radical and one free carboxyl radical.

12. The method of forming a monomeric tetrahydrophthalic acid half estercompound comprising esterifying a saturated fatty acid monoglyceridewith one carboxyl radical of an acid selected from the group consistingof lnaleic acid, fumarie acid and anhydrides thereof to form a halfester therewith, and then condensing said half ester with a 1,3 diene toform a tetrahydrophthalic acid half ester containing at least one freehydroxyl radical and one free carboxyl radical.

l0 half ester therewith, and then condensing said pound comprishalfester with a 1,3 diene to form a tetrahydrotty acid monophthaiic acidhalf ester containingr at least one a1 of an acid free hydroxyl radicaland one free carboxyl ting of maleic acid, 5 radical.

n condensing Said ALEXANDER C. KEYL. form a tetrahydro- ROBERT H. GEILS.

one free carboxyl 10 References Cited in the le of this patent g amonomeric tetra- UNITED STATES PATENTS ster compound com- Number NameDate g oil fatty acid mono- 1,860,730 Brooks May 31, 1932 xyl radical ofan acid 15 2,057,765 Brubaker Oct. 20, 1936` onsisting of maleic acid,2,251,297 Soday Aug. 5, 1941 rides thereof to form a Y 2,404,836Gerhartfff: July 3o, 1946

4. THE METHOD OF FORMING AN ALKYD RESIN COMPRISING DISSOLVING ATETRAHYDROPHTHALIC ACID HALFESTER OF A 12 TO 22 CARBON ATOM FATTY ACIDMONOESTER OF A POLYHYDROXY ALIPHATIC ALCOHOL HAVING AT LEAST ONE FREEHYDROXYL GROUP AND ONE FREE CARBOXYL GROUP IN A SOLVENT AND HEATING THESOLUTION AND THEREBY AZEOTROPICALLY DISTILLING SAID SOLVENT AND WATER OFCONDENSATION FROM THE SOLUTION.